The present invention is related to a selenating reagent.
Recently many syntheses of compounds containing selenium have been studied and reported because of the interesting reactivities and their potential pharmaceutical significance. Several methods for the synthesis of selenium-containing compounds using various types of selenating reagents have been developed. The alkali metal salts of hydrogen selenide, which can be readily prepared in situ by the reaction of elemental selenium and a reducing reagent (such as Li, LiBEt3H, Na, NaBH4, NaBEt3H, and iBu2AlH) have often been used as selenating reagents for the introduction into organic molecules.
However, the use of these salts as selenating reagents has been limited to the synthesis of dialkyl diselenides, dialkyl selenides, selenothiocarbamates, selenoamides, and certain other applications. A selenating reagent, capable of preparing a wide range of selenium-containing compounds, has not been reported.
The synthesis of diacyl selenides has been infrequently reported. Jensen, K. A.; Bøje, L.; Henriksen, L. Acta Chem. Scand., 1972, 26, 1465 reported the existence of unstable benzoyl selenide, which was obtained by the elimination of hydrogen selenide from selenobenzoic acid at room temperature. The benzoyl selenide was in turn transformed into dibenzoyl diselenide and bis(selenobenzoate). Kageyama, H.; Kido, K.; Kato, S.; Murai, T. J. Chem. Soc., Perkin Trans. 1, 1994, 1083 reported the preparation of diacyl selenides by the reaction of O-silyl selenocarboxylates with acyl chorides. Ishihara, H.; Sato, S.; Hirabayashi, Y. Bull. Chem. Soc. Jpn, 1977, 50, 3007 described the preparation of diacyl selenides. However, these methods all required many steps, while the present method is a one-pot reaction from which could be easily isolated diacyl selenides in very high yields using silica gel flash column chromatography. Until now it has been relatively difficult to be obtain aliphatic diacyl selenides because of their instability.
Synthesis examples of diacyl diselenides include: (a) Ishihara, H.; Hirabayashi, Y. Chem. Lett., 1976, 203. (b) Wang, J.-X.; Cui, W.-F.; Hu, Y.-L.; Zang, S.-S. J. Chem. Res. (S), 1990, 230. (c) Nishiyama, Y.; Katsuura, A.; Negoro, A.; Hamanaka, S.; Miyoshi, N.; Yamana, Y.; Ogawa, A.; Sonoda, N. J. Org. Chem., 1991, 56, 3776. (d) Niyomura, O.; Tani, K.; Kato, S., Heteroatm Chem., 1999, 10, 373. (e) Niyomura, O.; Kato, S.; Inagaki, S., J. Am. Chem. Soc., 2000, 122, 2132
Synthesis of glutaric selenoanhydride was reported in Koketsu, M.; Hiramatsu, S.; Ishihara, H. Chem. Lett., 1999, 485.
There is only one additional example of the synthesis of a γ-Selenobutyrolactone in the literature. That is Günther, W. H. H. J. Org. Chem., 1966, 31, 1202.
An example of N-alkyl diselenocarbamate synthesis; Henriksen, L. Int. J. Sulfur Chem., 1973, 8, 389. Carbodiimide was obtained via oxidation of selenourea using NaIO4 in quantitative yield. This method involved the reverse reaction.
Selenoureas and selenothiocarbamates bearing limited types of functional groups has been synthesized by using sodium hydrogen selenide. Klayman, D. L.; Shine, R. J. J. Org. Chem., 1969, 34, 3549.